Nucleophilic thiol-Michael chemistry and hyperbranched (co)polymers: Synthesis and ring-opening metathesis (co)polymerization of novel difunctional exo-7-oxanorbornenes with in situ inimer formation
Nucleophile-initiated thiol-Michael chemistry was employed to prepare a series of mono- and di-functional exo-7-oxanorbornenes from the reaction between mono- or dithiols with 2-((3aR,7aS)-1,3-dioxo-3a,4,7,7a-tetrahydro-1H-4,7-epoxyisoindol-2(3H)-yl)ethyl acrylate. Homopolymerization of the difuncti...
| Main Authors: | , , , |
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| Format: | Journal Article |
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2013
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| Online Access: | http://hdl.handle.net/20.500.11937/2968 |
| _version_ | 1848744099851534336 |
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| author | Liu, M. Tan, B. Burford, R. Lowe, Andrew |
| author_facet | Liu, M. Tan, B. Burford, R. Lowe, Andrew |
| author_sort | Liu, M. |
| building | Curtin Institutional Repository |
| collection | Online Access |
| description | Nucleophile-initiated thiol-Michael chemistry was employed to prepare a series of mono- and di-functional exo-7-oxanorbornenes from the reaction between mono- or dithiols with 2-((3aR,7aS)-1,3-dioxo-3a,4,7,7a-tetrahydro-1H-4,7-epoxyisoindol-2(3H)-yl)ethyl acrylate. Homopolymerization of the difunctional species, bis(2-((3aR,7aS)-1,3-dioxo-3a,4,7,7a-tetrahydro-1H-4,7-epoxyisoindol-2(3H)-yl)ethyl)-3,3′-((1,4-phenylenebis(methylene))bis (sulfanediyl))dipropanoate (M1), with Grubbs' first generation catalyst, RuCl2(PCy3)2CHPh, yields a hyperbranched polymer with up to 90% of polymerizable C C bonds consumed as judged by 1H NMR spectroscopy. SEC analysis is consistent with the formation of a hyperbranched structure with an absolute weight average molecular weight (Mw), as measured by static light scattering in CH2Cl2, determined to be 381 000. Bis(2-((3aR,7aS)-1,3-dioxo-3a,4,7,7a-tetrahydro-1H-4,7-epoxyisoindol-2(3H)-yl)ethyl)-3,3′-((thiobis(ethane-2,1-diyl))bis (sulfanediyl))dipropanoate (M2) could not be polymerized with the Grubbs' 1st generation catalyst but rapidly polymerized with 50% conversion of monomeric C C bonds with the Grubbs' 3rd generation species. Bis(2-((3aR,7aS)-1,3-dioxo-3a,4,7,7a-tetrahydro-1H-4,7-epoxyisoindol-2(3H)-yl)ethyl)-7,10-dioxa-4,13-dithiahexadecane-1,16-dioate (M3), in a similar fashion to M1, could be readily homopolymerized to high conversion with the 1st generation species giving organosoluble material.The statistical copolymerization of M1 or M3 with a series of monofunctional monomers containing pyrrole, fluoro, POSS and fluorene functionality is demonstrated. Copolymers of variable composition are readily prepared with the Grubbs' 1st generation catalyst with, in general, C C bond conversions in excess of 90%. Finally, the preparation of novel linear-hyperbranched AB diblock copolymers is demonstrated via the sequential polymerization of a monofunctional sugar derivative, (2S,3S,4S,5R,6R)-6-((3-(2-((3aR,7aS)-1,3-dioxo-3a,4,7,7a-tetrahydro-1H-4,7-epoxyisoindol-2(3H)-yl)ethoxy)-3-oxopropyl)thio) tetrahydro-2H-pyran-2,3,4,5-tetrayl tetraacetate (M8) which yields a well-defined linear homopolymer, as judged by SEC, followed by chain extension with the difunctional substrate M3. |
| first_indexed | 2025-11-14T05:56:05Z |
| format | Journal Article |
| id | curtin-20.500.11937-2968 |
| institution | Curtin University Malaysia |
| institution_category | Local University |
| last_indexed | 2025-11-14T05:56:05Z |
| publishDate | 2013 |
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| spelling | curtin-20.500.11937-29682017-09-13T14:31:38Z Nucleophilic thiol-Michael chemistry and hyperbranched (co)polymers: Synthesis and ring-opening metathesis (co)polymerization of novel difunctional exo-7-oxanorbornenes with in situ inimer formation Liu, M. Tan, B. Burford, R. Lowe, Andrew Nucleophile-initiated thiol-Michael chemistry was employed to prepare a series of mono- and di-functional exo-7-oxanorbornenes from the reaction between mono- or dithiols with 2-((3aR,7aS)-1,3-dioxo-3a,4,7,7a-tetrahydro-1H-4,7-epoxyisoindol-2(3H)-yl)ethyl acrylate. Homopolymerization of the difunctional species, bis(2-((3aR,7aS)-1,3-dioxo-3a,4,7,7a-tetrahydro-1H-4,7-epoxyisoindol-2(3H)-yl)ethyl)-3,3′-((1,4-phenylenebis(methylene))bis (sulfanediyl))dipropanoate (M1), with Grubbs' first generation catalyst, RuCl2(PCy3)2CHPh, yields a hyperbranched polymer with up to 90% of polymerizable C C bonds consumed as judged by 1H NMR spectroscopy. SEC analysis is consistent with the formation of a hyperbranched structure with an absolute weight average molecular weight (Mw), as measured by static light scattering in CH2Cl2, determined to be 381 000. Bis(2-((3aR,7aS)-1,3-dioxo-3a,4,7,7a-tetrahydro-1H-4,7-epoxyisoindol-2(3H)-yl)ethyl)-3,3′-((thiobis(ethane-2,1-diyl))bis (sulfanediyl))dipropanoate (M2) could not be polymerized with the Grubbs' 1st generation catalyst but rapidly polymerized with 50% conversion of monomeric C C bonds with the Grubbs' 3rd generation species. Bis(2-((3aR,7aS)-1,3-dioxo-3a,4,7,7a-tetrahydro-1H-4,7-epoxyisoindol-2(3H)-yl)ethyl)-7,10-dioxa-4,13-dithiahexadecane-1,16-dioate (M3), in a similar fashion to M1, could be readily homopolymerized to high conversion with the 1st generation species giving organosoluble material.The statistical copolymerization of M1 or M3 with a series of monofunctional monomers containing pyrrole, fluoro, POSS and fluorene functionality is demonstrated. Copolymers of variable composition are readily prepared with the Grubbs' 1st generation catalyst with, in general, C C bond conversions in excess of 90%. Finally, the preparation of novel linear-hyperbranched AB diblock copolymers is demonstrated via the sequential polymerization of a monofunctional sugar derivative, (2S,3S,4S,5R,6R)-6-((3-(2-((3aR,7aS)-1,3-dioxo-3a,4,7,7a-tetrahydro-1H-4,7-epoxyisoindol-2(3H)-yl)ethoxy)-3-oxopropyl)thio) tetrahydro-2H-pyran-2,3,4,5-tetrayl tetraacetate (M8) which yields a well-defined linear homopolymer, as judged by SEC, followed by chain extension with the difunctional substrate M3. 2013 Journal Article http://hdl.handle.net/20.500.11937/2968 10.1039/c3py00110e restricted |
| spellingShingle | Liu, M. Tan, B. Burford, R. Lowe, Andrew Nucleophilic thiol-Michael chemistry and hyperbranched (co)polymers: Synthesis and ring-opening metathesis (co)polymerization of novel difunctional exo-7-oxanorbornenes with in situ inimer formation |
| title | Nucleophilic thiol-Michael chemistry and hyperbranched (co)polymers: Synthesis and ring-opening metathesis (co)polymerization of novel difunctional exo-7-oxanorbornenes with in situ inimer formation |
| title_full | Nucleophilic thiol-Michael chemistry and hyperbranched (co)polymers: Synthesis and ring-opening metathesis (co)polymerization of novel difunctional exo-7-oxanorbornenes with in situ inimer formation |
| title_fullStr | Nucleophilic thiol-Michael chemistry and hyperbranched (co)polymers: Synthesis and ring-opening metathesis (co)polymerization of novel difunctional exo-7-oxanorbornenes with in situ inimer formation |
| title_full_unstemmed | Nucleophilic thiol-Michael chemistry and hyperbranched (co)polymers: Synthesis and ring-opening metathesis (co)polymerization of novel difunctional exo-7-oxanorbornenes with in situ inimer formation |
| title_short | Nucleophilic thiol-Michael chemistry and hyperbranched (co)polymers: Synthesis and ring-opening metathesis (co)polymerization of novel difunctional exo-7-oxanorbornenes with in situ inimer formation |
| title_sort | nucleophilic thiol-michael chemistry and hyperbranched (co)polymers: synthesis and ring-opening metathesis (co)polymerization of novel difunctional exo-7-oxanorbornenes with in situ inimer formation |
| url | http://hdl.handle.net/20.500.11937/2968 |